JP6844279B2 - Metal / resin composite structure and its manufacturing method - Google Patents

Description

The present invention relates to a metal / resin composite structure formed by joining a metal member and a thermoplastic resin member composed of a thermoplastic resin composition, a method for producing the same, and a resin composition used for the metal / resin composite structure. And resin members.

From the viewpoint of weight reduction of various parts, a highly heat-resistant resin member is used as a substitute for a metal member. However, when it is difficult to replace all metal members with resin due to problems such as mechanical strength, a composite structure obtained by joining and integrating the metal member and the resin member (hereinafter, metal / resin composite structure). ) Is used. Examples of such a metal / resin composite structure include a method of irradiating the surface of a metal member with a laser to form minute recesses and joining them by an anchor effect (Patent Documents 1, 2, and 3). ). Since the surface of the metal member formed by laser irradiation is very rough, the frictional force on the joint surface with the resin is improved, and the durability is maintained against the shearing force acting in the same direction as the joint surface. However, when the thermal cycle test is performed, interfacial peeling is likely to occur at the submicron level as the resin expands and contracts, and therefore, the adhesion between the metal molded body and the resin molded body, especially when the cold cycle is applied. There was a problem that the adhesion (called cold heat cycle resistance) was low.

Therefore, when forming a recess by laser irradiation on the surface of the metal member to be joined to the thermoplastic resin member, the angle formed by the surface of the metal member and the side surface of the recess is increased in the range of 10 to 55 ° C. It has become possible to provide a metal-resin bonded molded product having adhesive strength, particularly excellent cold-heat cycle resistance (see Patent Document 4). However, in the metal-resin bonded molded product, excellent adhesion is obtained by forming a portion that becomes a catch after solidification by flowing the resin into the recess of the metal member, so that the metal member flows into the recess. There is a growing demand for resin materials with higher fluidity so that it is easier to use.

Regarding the improvement of the resin member, for example, it is treated with a chemical solution such as an erosive aqueous solution or an erosive suspension by an aluminum alloy or magnesium alloy having a recess with a number average inner diameter of 10 to 80 nm on the surface, or an anodic oxidation method. Polyphenylene sulfide and a specific ratio of maleic anhydride-modified ethylene-based copolymer, glycidyl methacrylate-modified ethylene-based copolymer, and glycidyl ether-modified ethylene-based copolymer in an aluminum alloy having recesses with a number average inner diameter of 10 to 80 nm on the surface. A composite obtained by injection molding a resin composition containing one or more kinds of polyolefin resins selected from the group consisting of ethylene alkyl acrylate-based copolymers and ethylene alkyl acrylate-based copolymers, and fixing the resin composition in the recesses in a state of being infiltrated. It is known (see Patent Document 5). Since the inner diameter of the fine recesses on the metal surface formed by any of the treatment methods is very fine, it is difficult for the resin composition to penetrate, and therefore the metal parts and the resin member composed of the resin composition The adhesion was not sufficient.

Therefore, regardless of the means such as laser processing, treatment method using an erosive aqueous solution or an erosive suspension, and anodization method, the resin material can easily infiltrate into the fine uneven portion formed by surface roughening. There was a need to develop a resin material with better fluidity.

International Publication 2007/07263 Pamphlet JP-A-2010-167475 Japanese Unexamined Patent Publication No. 2013-107273 Japanese Unexamined Patent Publication No. 2015-100959 JP-A-2007-050630

Therefore, the problem to be solved by the present invention is a metal having excellent adhesion, which is formed by joining a metal member having a roughened surface and a thermoplastic resin member composed of a highly heat-resistant thermoplastic resin composition. It is an object of the present invention to provide a resin composite structure and a method for producing the same. Further, the present invention is a thermoplastic resin composition, which has excellent fluidity, and a thermoplastic resin member which is a molded body thereof can exhibit excellent adhesion to a metal part having fine uneven portions formed on its surface. An object of the present invention is to provide a thermoplastic resin member, which is formed by melt-molding the same and capable of exhibiting excellent adhesion to a metal part having fine uneven portions formed on the surface.

As a result of various studies by the inventors of the present application, the thermoplastic resin composition obtained by blending a phenol resin with a thermoplastic resin having a melting point of 160 ° C. or higher has excellent fluidity and fine uneven portions are formed on the surface. We have found that it is possible to provide a thermoplastic resin member that exhibits excellent adhesion to the metal parts, and have solved the present invention.

That is, the present invention is a metal / resin composite structure formed by joining a surface-roughened metal member and a thermoplastic resin member composed of a thermoplastic resin composition.
The metal member is aluminum, copper, magnesium, iron, titanium or an alloy containing them.
The thermoplastic resin composition comprises a thermoplastic resin (A) having a melting point of 160 ° C. or higher and a phenol resin (B) with respect to 100 parts by mass of the thermoplastic resin (A). The present invention relates to a metal / resin composite structure, which comprises molding a thermoplastic resin composition containing the above in the range of 0.05 to 20 parts by mass.

That is, the present invention is a metal / resin composite structure formed by joining a metal member whose surface has been roughened and a thermoplastic resin member composed of a thermoplastic resin composition.
The metal member is aluminum, copper, magnesium, iron, titanium or an alloy containing them.
The thermoplastic resin composition comprises a thermoplastic resin (A) having a melting point of 160 ° C. or higher and a phenol resin (B) with respect to 100 parts by mass of the thermoplastic resin (A). The present invention relates to a metal / resin composite structure, which comprises molding a thermoplastic resin composition containing the above in the range of 0.05 to 20 parts by mass.

Further, the present invention is a method for producing a metal / resin composite structure in which a surface-roughened metal member and a thermoplastic resin member composed of a thermoplastic resin composition are joined.
The metal member is aluminum, copper, magnesium, iron, titanium or an alloy containing them.
A feature is that a thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 160 ° C. or higher and a phenol resin (B) is melt-molded on a metal member at a melting point of the thermoplastic resin (A) or higher. The present invention relates to a method for producing a metal / resin composite structure.

Further, the present invention is a thermoplastic resin composition used for a metal / resin composite structure in which a surface-roughened metal member and a thermoplastic resin member composed of a thermoplastic resin composition are joined. ,
The metal member is aluminum, copper, magnesium, iron, titanium or an alloy containing them.
The thermoplastic resin composition is formed by blending a thermoplastic resin (A) having a melting point of 160 ° C. or higher and a phenol resin (B) as essential components, with respect to 100 parts by mass of the thermoplastic resin (A). The thermoplastic resin composition, characterized in that the phenol resin (B) is in the range of 0.05 to 20 parts by mass.

Further, the present invention is a thermoplastic resin member used for a metal / resin composite structure in which a surface-roughened metal member and a thermoplastic resin member composed of a thermoplastic resin composition are joined.
The metal member is aluminum, copper, magnesium, iron, titanium or an alloy containing them.
The thermoplastic resin composition is formed by blending a thermoplastic resin (A) having a melting point of 160 ° C. or higher and a phenol resin (B) as essential components, with respect to 100 parts by mass of the thermoplastic resin (A). , The range of 0.05 to 20 parts by mass of the phenol resin (B).
The present invention relates to a thermoplastic resin member, which is obtained by melt-molding a thermoplastic resin composition.

According to the present invention, a metal / resin composite structure having excellent adhesion, which is formed by joining a metal member whose surface has been roughened and a thermoplastic resin member composed of a thermoplastic resin composition, and a method for producing the same. To provide. Further, the present invention is a thermoplastic resin composition, which has excellent fluidity, and a thermoplastic resin member which is a molded body thereof can exhibit excellent adhesion to a metal part having fine uneven portions formed on its surface. And a thermoplastic resin member, which is formed by melt-molding the same and capable of exhibiting excellent adhesion to a metal part having fine uneven portions formed on the surface thereof, can be provided.

Explanatory drawing for showing the measurement reference on the fine concavo-convex surface in the cross section in the direction perpendicular to the surface of a metal member.

The metal / resin composite structure of the present invention is a metal / resin composite structure formed by joining a surface-roughened metal member and a thermoplastic resin member composed of a thermoplastic resin composition.
The metal member is aluminum, copper, magnesium, iron, titanium or an alloy containing them.
The thermoplastic resin composition comprises a thermoplastic resin (A) having a melting point of 160 ° C. or higher and a phenol resin (B) with respect to 100 parts by mass of the thermoplastic resin (A). It is characterized in that it is formed by molding a thermoplastic resin composition containing in the range of 0.05 to 20 parts by mass.

(Metal member)
The metal member constituting the metal / resin composite structure of the present invention has a fine uneven surface (hereinafter, simply referred to as a metal member surface) on the surface of the metal member (hereinafter, simply referred to as the metal member surface) to be joined to the thermoplastic resin member composed of the thermoplastic resin composition. Hereinafter, it has a fine uneven surface).

The metal / resin composite structure of the present invention is composed of a metal member and the resin composition by entering into the recesses of the fine concavo-convex surface in a molten state and solidifying the thermoplastic resin composition used in the present invention. The thermoplastic resin member is joined to form an interface between the metal member and the thermoplastic resin member (hereinafter, simply referred to as a metal-resin interface).

In the metal member used in the present invention, a fine concavo-convex surface is formed on the material surface of the metal portion due to surface roughness, and the distance between the concavo-convex portions is from a convex portion to an adjacent convex portion (hereinafter, referred to as “between convex portions”). The length is preferably in the range of 5 nm or more, more preferably in the range of 10 nm or more. The upper limit value is not particularly limited because it can flow even if the fluidity is low, but the range of 700 μm or less is preferable, and the range of 500 μm or less is more preferable because the adhesion tends to be improved when the unevenness density is high. .. When the length between the convex portions is within the above range, the thermoplastic resin composition used in the present invention can enter the concave portions of the fine concavo-convex surface with good adhesion, and exhibits excellent adhesion at the metal-resin interface. can do. Further, it is preferable that the distance between the uneven portions has periodicity because better adhesion can be exhibited at the metal-resin interface.

Further, the height difference of the uneven portion is preferably in the range of 50 nm or more, more preferably 100 nm or more. The adhesion strength tends to improve as the height difference increases, but 500 μm or less is preferable in consideration of filling the uneven portion with a resin so as not to generate voids.

The length between the convex portions is adjacent to the length between the convex portions from the top of the convex portions based on a photograph taken by an electron microscope or a laser microscope of a cross section cut in the direction perpendicular to the fine uneven surface of the surface of the metal member. After selecting at least 50 points between the two points up to the top of the convex portion, measure the length of the component in the direction parallel to the fine concavo-convex surface of the metal member surface (reference numeral x in FIG. 1), and average the numbers. It can be calculated as a value. As for the height difference of the uneven portion, at least 50 points are selected between the two points from the top of the convex portion to the bottom surface of the adjacent concave portion based on the photograph of the cross section taken by an electron microscope or a laser microscope. The length of the component in the direction perpendicular to the fine uneven surface of the surface of the metal member (reference numeral y in FIG. 1) can be measured and obtained as the average value thereof.

Further, the uneven shape of the fine uneven surface is not particularly limited, and may be formed as a concave portion having a pore diameter smaller than the distance between the convex portions by surface roughness described later, and the surface roughening is further promoted. The shape may be observed in a forested state as a rounded convex portion, that is, a cylinder having a spherical shape or a smooth end, or a protrusion having a three-dimensional aspect such as a wart shape or a karinto shape.

Examples of the type of metal constituting the metal member include aluminum, copper, magnesium, iron, titanium, and alloys containing them. More specifically, iron, for example, stainless steel, steel, etc., containing iron as a main component, that is, 20% by mass or more, more preferably 50% by mass or more, still more preferably 80% by mass, and other carbons and silicons. , Manganese, chromium, tungsten, molybdenum, phosphor, titanium, vanadium, nickel, zirconium, boron, etc. (hereinafter, iron alloy), aluminum, aluminum as the main component, copper, manganese, silicon, magnesium , Zinc, nickel-containing alloys (hereinafter, aluminum alloys), magnesium, magnesium-based alloys, zinc, aluminum, zirconium-containing alloys (hereinafter, magnesium alloys), copper, and copper-based main components. In addition, alloys containing zinc, tin, phosphorus, nickel, magnesium, silicon, and chromium (hereinafter referred to as copper alloys), titanium, and titanium as the main component, as well as copper, manganese, silicon, magnesium, zinc, and nickel. Examples thereof include alloys containing (hereinafter, titanium alloys). Of these, iron, iron alloys, aluminum alloys, magnesium alloys, copper alloys and titanium alloys are more preferable, and iron alloys, aluminum alloys and magnesium alloys are more preferable.

It is preferable that the metal member used in the present invention has a surface roughness and has a fine uneven surface on the surface. As the surface roughness method, a known method can be used without limitation, and examples thereof include three types of methods.

(1) Immersion method with an erosive aqueous solution or an erosive suspension. It is preferable to have a shape in which fine uneven surfaces are formed on the metal surface, and more preferably, the metal surface has a shape in which a large number of recesses are formed, and the recesses have a number average inner diameter of 3 μm or less. Similarly, it is more preferable that the concave portion has a number average inner diameter of 10 nm to 3 μm.

(2) Anodizing method. By mainly forming a metal oxide layer on the surface, it is preferable to form a large number of openings having a number average inner diameter of 1 μm or less on the surface layer, and similarly, openings having a number average inner diameter of 1 nm to 1 μm. It is more preferable to form a portion, and it is more preferable to form an opening having a number average inner diameter range of 10 to 200 nm.

(3) A method of forming irregularities on a metal surface by pressing a die punch having irregularities created by mechanical cutting, for example, diamond abrasive grain grinding or blasting, or creating an uneven shape on a metal surface by sandblasting or laser processing. how to. Mainly, it is preferable to process the surface into a large number of recesses, and when forming continuous recesses such as the number average inner diameter of the recesses or laser machining, the width is preferably in the range of 1 to 1000 μm, and further 10 to 10 More preferably, it is in the range of 800 μm.

Before forming the above-mentioned fine uneven surface, the metal member is processed into a predetermined shape by plastic working such as cutting, pressing, punching, cutting, grinding, electric discharge machining and the like. Is preferable.

A primer layer may be formed on the surface of the metal member that has been surface-treated with metal. The material constituting the primer layer is not particularly limited, but is usually composed of a primer resin material containing a resin component. The primer resin material is not particularly limited, and known ones can be used. Specific examples thereof include known polyolefin-based primers, epoxy-based primers, and urethane-based primers. The method for forming the primer layer is not particularly limited, and for example, a solution of the above-mentioned primer resin material or an emulsion of the above-mentioned primer resin material can be applied to the metal member subjected to the above-mentioned surface treatment to form the primer layer. Examples of the solvent used for making the solution include toluene, methyl ethyl ketone (MEK), dimethylformamide (DMF) and the like. Examples of the medium for the emulsion include an aliphatic hydrocarbon medium and water.

Examples of the thermoplastic resin (A) used in the present invention include thermoplastic resins having a melting point of 160 ° C. or higher, preferably 210 ° C. or higher, more preferably 210 ° C. or higher, and specifically, polypropylene resin or PMP. Such as, a polyolefin resin having a melting point of 160 ° C. or higher, preferably a melting point of 210 to 250 ° C., a polyamide 6 (6-nylon) resin, a polyamide 66 (6,6-nylon) resin or a polyamide 12 (12-nylon). An aromatic skeleton having a melting point of 210 ° C. or higher, preferably 210 to 310 ° C., such as a polyamide resin having an aliphatic skeleton such as a resin, a polyamide 6T (6T-nylon) resin, or a polyamide 9T (9T-nylon) resin. The melting point of a polyamide resin having an aromatic skeleton (hereinafter, a polyamide resin having an aromatic skeleton may be referred to as an aromatic polyamide resin), a polybutylene terephthalate resin, a polyisobutylene terephthalate resin, a polyethylene terephthalate resin, or a polycyclohexene terephthalate resin is 210 ° C. As described above, a polyester resin preferably in the range of 210 to 280 ° C., a polyether ether ketone resin having a melting point in the range of 300 to 390 ° C., or a parahydroxybenzoic acid having a parahydroxybenzoic acid in the skeleton has a melting point of 300 ° C. or higher, preferably 300 ° C. or higher. Heat having a melting point of 210 ° C. to 390 ° C., such as a liquid crystal polymer having a melting point of 300 ° C. to less than a thermal decomposition temperature (380 ° C.) or a syndiotactic polystyrene resin having a melting point of 210 ° C. or higher, preferably 210 ° C. to 280 ° C. Examples thereof include so-called general-purpose engineering plastics and super-engineering plastics such as plastic resins, and among them, polybutylene terephthalate resin and aromatic polyamide resin having excellent flame retardancy and dimensional stability are preferable.

In the present invention, the "melting point" refers to the melting peak temperature measured by differential scanning calorimetry (DSC) in accordance with the method of JIS 7121 (1999) 9.1 (1).

The thermoplastic resin composition used in the present invention contains a phenol resin (B) as an essential component.

Next, the phenol resin used in the present invention refers to a thermoplastic polymer having a phenol skeleton, and either a novolak type phenol resin or a bisphenol type phenol resin can be used as a preferable one, and a novolak type phenol resin is more preferable. The phenol resin (B) is distinguished from the thermoplastic resin (A) in that it does not have a melting point of 160 ° C. or higher.

In a phenol resin, a phenol compound and an aldehyde compound are generally reacted at 40 to 150 ° C. for 1 to 5 hours in the presence of an acid catalyst, and then subjected to a normal pressure dehydration or a vacuum dehydration step to obtain residual water. Is removed from the reaction system, and the condensate in the reaction system is dissolved in a solvent such as methanol. The ratio of [aldehyde compound] / [phenol compound] is not particularly limited within a known range, but is preferably in the range of 0.3 to 1.0 in terms of molar ratio. The phenol skeleton is derived from the raw material phenolic compound. The phenol compound is not particularly limited as long as it is known, and for example, alkylphenols such as phenol, naphthol or cresol, xylenol, ethylphenol, butylphenol and octylphenol; polyhydric phenols such as resorcin and catechol; bisphenol A, Bisphenols such as bisphenol F, bisphenol S, bisphenol E, thiobisphenol, bis (hydroxyphenyl) ether, dihydroxybenzophenone, bisphenol fluorene; halogenated phenol, phenylphenol, aminophenol and the like can be mentioned. Further, these phenol compounds are not limited to only one type in their use, and two or more types can be used in combination.

The aldehyde compound can be used without particular limitation as long as it is generally used in the production of phenol resin, and examples thereof include formaldehyde, paraformaldehyde, formaldehyde such as trioxane, acetaldehyde, and hexamethylenetetramine. Can be done.

As the acid catalyst, acids used in the production of novolak type phenol resin can be used, and examples thereof include formic acid, hydrochloric acid, phosphoric acid, sulfuric acid, paratoluenesulfonic acid, and phenolsulfonic acid.

The compounding of the phenol resin can lower the viscosity of the thermoplastic resin composition and improve the fluidity during molding, so that the composition flows into the details of the unevenness of the adhesive surface of the metal member and anchors. The effect can be increased. Further, due to the presence of the hydroxyl group, a large number of hydrogen bonds can be formed on the adhesive surface of the metal member to improve the adhesive force. Further, even in a high temperature and high humidity environment, it is possible to suppress the infiltration of water into the adhesive surface and develop a high adhesive retention rate.

The hydroxyl group equivalent of the phenol resin is preferably high, and the range may be a known range, but it is in the range of 80 to 200 g / equivalent because it is possible to further improve the adhesive force or the adhesive force. Those in the range of 100 to 180 g / equivalent are more preferable, and those in the range of 110 to 150 g / equivalent are further preferable.

The phenol resin may be either a solid type or a solvent type, but it is more preferable to use the solid type. When using the solid type, it is preferable to use one having a softening point in the range of 50 to 180 ° C, and more preferably one having a softening point in the range of 70 to 150 ° C. When using the solvent type, it is preferable to use a solvent type having a viscosity (as a solid content 60% MEK solution) in the range of 50 to 2000 (25 ° C., mPa · s), and 70 to 1500 (25 ° C., mPa · s). It is more preferable to use the one in the range of.

The proportion of the phenol resin (B) in the thermoplastic resin composition is preferably in the range of 0.05 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A), and is 0.1. It is preferably in the range of ~ 15 parts by mass, and more preferably in the range of 0.5 to 10 parts by mass. Within the above range, both excellent metal member adhesiveness and low gas properties during melt-kneading and melt-molding can be achieved at the same time.

The thermoplastic resin composition of the present invention may contain a filler as an optional component, if necessary. As these fillers, known and commonly used materials can be used as long as they do not impair the effects of the present invention, and have various shapes such as fibrous ones and non-fibrous ones such as granular and plate-like ones. Examples include fillers. Specifically, glass fibers, carbon fibers, silane glass fibers, ceramic fibers, aramid fibers, metal fibers, potassium titanate, silicon carbide, calcium silicate, warastonite and other fibers, and natural fibers and other fibrous fillers are used. Can also be used, glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, mica, talc, attapulsite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, zeolite, milled fiber , Non-fibrous fillers such as calcium sulfate can also be used.

In the present invention, the filler is not an essential component, and when added, the content thereof is not particularly limited as long as the effect of the present invention is not impaired. The content of the filler is, for example, preferably in the range of 1 to 600 parts by mass, and more preferably in the range of 10 to 200 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). In such a range, the resin composition is preferable because it exhibits good mechanical strength and moldability.

The thermoplastic resin composition of the present invention may contain a silane coupling agent as an optional component, if necessary. The silane coupling agent is not particularly limited as long as the effects of the present invention are not impaired, but a silane coupling agent having a functional group that reacts with a carboxy group, for example, an epoxy group, an isocyanato group, an amino group or a hydroxyl group is preferable. Can be mentioned. Examples of such a silane coupling agent include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Containing alkoxysilane compound, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane , Γ-Isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane and other isocyanato group-containing alkoxysilane compounds, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) amino Examples thereof include amino group-containing alkoxysilane compounds such as propyltrimethoxysilane and γ-aminopropyltrimethoxysilane, and hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. Although the silane coupling agent is not an essential component in the present invention, when it is added, the mixing ratio thereof is not particularly limited as long as the effect of the present invention is not impaired, but with respect to 100 parts by mass of the thermoplastic resin (A). The range is preferably in the range of 0.01 to 10 parts by mass, and more preferably in the range of 0.1 to 5 parts by mass. In such a range, the resin composition is preferable because it has good corona resistance and moldability, particularly mold releasability, and the molded product exhibits excellent adhesiveness to the epoxy resin, and the mechanical strength is further improved.

The thermoplastic resin composition of the present invention may contain a thermoplastic elastomer as an optional component, if necessary. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluoroelastomers, and silicone-based elastomers, and among them, polyolefin-based elastomers are preferable. When these elastomers are added, the mixing ratio thereof is not particularly limited as long as the effects of the present invention are not impaired, but is in the range of 0.01 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). It is preferably in the range of 0.1 to 25 parts by mass, and more preferably in the range of 0.1 to 25 parts by mass. In such a range, the impact resistance of the obtained thermoplastic resin composition is improved, which is preferable.

The polyolefin-based elastomer is, for example, a homopolymerization of α-olefins or a copolymerization of different α-olefins, and when a functional group is further imparted, the α-olefin and a vinyl polymerizable compound having a functional group are used. It can be obtained by copolymerization. Examples of the α-olefin include those in the range of 2 to 8 carbon atoms such as ethylene, propylene and butene-1. The functional group includes a carboxy group, an acid anhydride group represented by the formula − (CO) O (CO) −, an ester thereof, an epoxy group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, or an oxazoline group. And so on.

Specific examples of the vinyl polymerizable compound having such a functional group include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid ester and their alkyl esters, maleic acid and fumaric acid. Examples thereof include acids, itaconic acids and other α, β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono or diesters and their acid anhydrides, etc.), and glycidyl (meth) acrylates. Among these, ethylene-propylene copolymers and ethylene-butene copolymers having at least one functional group selected from the group consisting of the above-mentioned epoxy group, carboxy group, and acid anhydride group are mechanically used. It is preferable from the viewpoint of improving strength, particularly toughness and impact resistance.

When the elastomer has an epoxy group as a functional group, it reacts with the phenol resin during melt-kneading. Therefore, the upper limit of the mixing ratio is 10 with respect to 100 parts by mass of the thermoplastic resin (A). It is preferably in the range of parts by mass or less, more preferably in the range of 5 parts by mass, and particularly preferably in the range of 0 parts by mass, that is, substantially no elastomer having such an epoxy group is used. preferable.

Further, the thermoplastic resin composition of the present invention may contain a synthetic resin other than the thermoplastic resin (A) as an optional component in addition to the above components, depending on the intended use. Examples of the synthetic resin include synthetic resins such as crystalline thermoplastic resins having a melting point of less than 160 ° C. and amorphous thermoplastic resins, and specific examples thereof include polyethylene resins, polyvinyl chloride resins, and polystyrene resins. , AS resin, ABS resin, methacrylic resin, polycarbonate resin, modified polyphenylene ether (mPPE) resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyetherimide resin and the like. The mixing ratio of these resins differs depending on the purpose of each and cannot be unconditionally specified, but it is in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). It may be appropriately adjusted and used according to the purpose and application so as not to impair the effect of the invention.

In addition, the thermoplastic resin composition of the present invention also contains a colorant, an antistatic agent, an antioxidant, a heat-resistant stabilizer, an ultraviolet stabilizer, an ultraviolet absorber, a foaming agent, a flame retardant, a flame retardant aid, and a mold release agent. Known and commonly used additives such as agents, rust preventives, and coupling agents may be contained as optional components, if necessary. These additives are not essential components, and the mixing ratio thereof is, for example, preferably in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A), which impairs the effect of the present invention. It may be adjusted appropriately according to the purpose and application so as not to occur.

In the method for producing a thermoplastic resin composition of the present invention, the thermoplastic resin (A) and the phenol resin (B) are blended as essential components and melt-kneaded at a temperature equal to or higher than the melting point of the thermoplastic resin (A).

A preferable method for producing the thermoplastic resin composition of the present invention is to use the thermoplastic resin (A), each of the essential components of the phenol resin (B), and, if necessary, a filler so as to have the above-mentioned compounding ratio. Arbitrary components such as powder, pellets, and strips are put into a ribbon blender, Henschel mixer, V blender, etc. in various forms for dry blending, and then a Banbury mixer, mixing roll, single-screw or twin-screw extruder. And a temperature range in which the resin temperature is equal to or higher than the melting point of the thermoplastic resin (A), preferably a temperature range in which the melting point is + 10 ° C. or higher, more preferably a melting point of + 10 ° C. to a melting point of +100. It can be produced through a step of melt-kneading in a temperature range of ° C., more preferably in a temperature range of melting point +20 to melting point +50 ° C. Each component may be added to and mixed with the melt kneader at the same time, or may be divided.

The thermoplastic resin composition of the present invention obtained by melt-kneading in this way contains the thermoplastic resin (A) which is an essential component, the phenol resin (B), an optional component added as necessary, and the origin thereof. It is a melt mixture containing components, and after the melt kneading, it is processed into pellets, chips, granules, powders, etc. by a known method, and then pre-dried at a temperature of 100 to 150 ° C. as necessary. It is preferable to use it for various moldings.

The thermoplastic resin composition of the present invention produced by the above-mentioned production method uses a thermoplastic resin (A) as a matrix, and in the matrix, the phenol resin (B) which is an essential component, a component derived from the phenol resin (B), and necessary components. It forms a morphology in which arbitrary components added according to the above are dispersed. The thermoplastic resin composition used in the present invention flows during melting by adding a phenol resin to a thermoplastic resin having a melting point of 160 ° C. or higher to break the crystallinity of the thermoplastic resin as a matrix and lower the crystallization temperature. It is considered that the property can be improved, and as a result, it becomes possible to penetrate into the concave portion of the fine uneven portion formed by the surface roughening treatment on the metal member with good wettability, and further excellent adhesiveness is provided at the metal-resin interface. It is thought that it can be demonstrated. Since the adhesive effect is the principle of holding the metal-resin interface by the physical holding force called the anchor effect, if the resin itself is a crystalline thermoplastic resin, the surface of the metal itself is roughened. As long as it is used, the effect can be exhibited without any problem regardless of the material, but the effect of improving the fluidity at the time of melting tends to be higher as the melting point of the thermoplastic resin is higher, so that the melting point is preferably 160 ° C. or higher. A thermoplastic resin in the range of 210 ° C. or higher, more preferably 210 to 390 ° C. is preferably used in the present invention.

The metal / resin composite structure formed by joining the metal member and the thermoplastic resin member composed of the thermoplastic resin composition of the present invention comprises a thermoplastic resin (A) and a phenol resin (B). It is obtained by melt-molding the containing thermoplastic resin composition into a metal member at a temperature equal to or higher than the melting point of the thermoplastic resin (A). The melt molding method of the thermoplastic resin member used in the present invention on the surface of a metal material is an injection molding, compression molding, composite, sheet, pipe or the like extrusion molding, drawing molding, blow molding of the thermoplastic resin composition used in the present invention. It is possible to perform various melt molding such as transfer molding, but since it is particularly excellent in releasability, it is possible to use the so-called metal insert molding method in which a metal member is set in the mold in advance and injection molding is performed. preferable. Regardless of which molding method is used, various molding conditions can be molded by a usual general method. For example, in an injection molding machine, the resin temperature is in a temperature range equal to or higher than the melting point of the thermoplastic resin (A), preferably in a temperature range of the melting point + 10 ° C. or higher, more preferably in a temperature range of melting point + 10 ° C. to melting point + 100 ° C., more preferably. After undergoing a step of melting the thermoplastic resin composition in a temperature range of +20 to +50 ° C., the resin discharge port may be injected into a mold in which a metal member is set for molding. At that time, the mold temperature may be set to a known temperature range, for example, room temperature (23 ° C.) to 300 ° C., preferably 40 to 200 ° C., and more preferably 120 to 180 ° C.

Examples of the main applications of the composite molded body include housings for various home appliances, mobile phones, electronic devices such as PCs (Personal Computers), protection / support members for box-shaped electrical / electronic component integration modules, and a plurality of components. Individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed boards, tuners, speakers , Microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, and other electrical and electronic parts; VTR parts , TV parts, irons, hair dryers, rice cooker parts, microwave parts, acoustic parts, audio / video equipment parts such as audio / laser discs / compact discs / DVD discs / Blu-ray discs, lighting parts, refrigerator parts, air conditioner parts, Household and office electrical product parts represented by typewriter parts, word processor parts, water supply parts for water heaters and baths, water supply equipment parts such as temperature sensors; office computer related parts, telephone equipment related parts, facsimile related parts, copying Machine-related parts, cleaning jigs, motor parts, writers, typewriters, and other machine-related parts: microscopes, binoculars, cameras, watches, and other optical equipment, precision machine-related parts; alternator terminals, alternator connectors , Brush holder, slip ring, IC regulator, potential meter base for light dial, relay block, inhibitor switch, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, Fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crank shaft position sensor, air flow meter, brake pad wear sensor, air conditioner Thermostat base, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, Dustriview Tar, starter switch, ignition coil and its bobbin, motor insulator, motor rotor, motor core, starter reel, wire harness for transmission, window washer nozzle, air conditioner panel switch board, fuel-related electromagnetic valve coil, fuse connector, horn terminal It can also be applied to automobile / vehicle-related parts such as insulating plates for electrical components, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, and ignition device cases, and various other applications.

The present invention will be described in more detail below with specific examples. In addition, parts and% are based on mass unless otherwise specified.

(Examples 1 to 9 and Comparative Examples 1 to 3) Production of Thermoplastic Resin Compositions Each material was uniformly mixed with a tumbler according to the composition components and blending amounts (all by mass) shown in Tables 1 to 3. After that, the compound material was put into a twin-screw extruder "TEX30α" with a vent from Japan Steel Works, Ltd., and the resin component discharge amount was 25 kg / hr, the screw rotation speed was 250 rpm, the set resin temperature was set to 330 ° C for PA resin, and PBT resin The temperature of the PP resin was set to 270 ° C. and the temperature of the PP resin was set to 200 ° C. The following various evaluation tests were conducted using these pellets. The results of the tests and evaluations are shown in Tables 1-3.

(Measurement Example 4) Adhesion Strength Experimental Method A metal test piece (length x width x thickness = 50 mm x 10 mm x 2 mm) subjected to the following roughening treatment is used for injection molding (mold temperature is 140 ° C. during PA molding). , 140 ° C for PBT molding, 60 ° C for PP molding), and a metal / resin composite structure (based on ISO19095 compliant Type-A type) so that the treated surface and the resin composition are vertically joined. Molded. A tensile test (tensile speed 1 mm / min) was carried out in the direction perpendicular to the joint surface of the obtained structure, and the obtained maximum stress value was taken as the adhesion strength.

Metal treatment (S): A metal piece was cut out from an aluminum plate (material: A1050) to the above-mentioned size, and the joint surface was further polished (abrasive paper roughness: No. 1000). When the joint surface after polishing was observed with an electron microscope, it was not observed that the surface was covered with recesses having a number average inner diameter of 100 nm or less. A hole is made in the end opposite to the joint surface of this aluminum piece, a copper wire coated with vinyl chloride is passed through a dozen pieces, and the copper wire is bent so that the aluminum pieces do not overlap each other. Can be hung at the same time.

7.5% of a commercially available aluminum alloy degreasing agent "NE-6 (manufactured by Meltex Inc.)" is put into water and then melted by heating at 75 ° C., and the above aluminum pieces are immersed for 5 minutes and washed thoroughly with water. did. Subsequently, a 10% caustic soda aqueous solution at 50 ° C. was prepared in another tank, and the aluminum piece was immersed therein for 0.5 minutes and washed thoroughly with water.

Subsequently, a 60% nitric acid solution at 90 ° C. was prepared in another tank, immersed for 15 seconds, and washed thoroughly with water. Subsequently, a 5% aqueous sulfuric acid solution at 20 ° C. was prepared in another tank, the anode of the DC power supply device "ASR3SD-150-500 (manufactured by Chuo Seisakusho)" was connected to the hole of the aluminum piece, and the cathode was the tank. It was anodized by constant current control to a current density of ^{5 A / dm 2} by connecting to a lead plate placed in. It was anodized for 40 minutes, washed with water, and placed in a warm air dryer at 60 ° C. for 1 hour to dry. One day later, one of the joint surfaces was photographed with a scanning electron microscope (magnification: 500,000 times), and 50 recesses were randomly selected from each image before measurement. The concave portions were periodically and continuously formed on the surface, the distance between the convex portions was 50 nm on average, the number average pore diameter was 30 μm, and the density of the concave portions was 10 per ^{100 nm 2.}

After the treatment, it was molded immediately and the adhesion strength (S1) was measured. Further, the adhesion strength (S2) was measured after being left for 200 hours in a constant temperature and high humidity (80 ° C., humidity 95%) environment. The evaluation was performed with n = 3 times, and the average value was taken.

Metal treatment (T): Laser groove processing was performed using a YAG laser marker device (“LAY-791DE” manufactured by Shibaura Eletech Co., Ltd.) as a metal test piece. Continuous grooves having a length of 10 mm, a depth of 150 μm, and a width of 100 μm were formed on the end face of the metal piece at intervals of 100 μm.

After the treatment, it was molded immediately and the adhesion strength (T1) was measured. Further, the adhesion strength (T2) was measured after being left for 200 hours in a constant temperature and high humidity (80 ° C., humidity 95%) environment. The evaluation was performed with n = 3 times, and the average value was taken.

The compounding ratios of the compounded resins and materials in Tables 1 to 3 represent parts by mass, and the following were used.
A-1: The aromatic polyamide (PA) resin was produced by the following method.
[Manufacturing Example 1]
1827 g (11.0 mol) of terephthalic acid, 2343 g (20.2 mol) of 1,6-hexanediamine, 1315 g (9.0 mol) of adipic acid, 30.5 g (0.25 mol) of benzoic acid, hypophosphorous acid 4.7 g of sodium monohydrate (0.08% by mass based on the raw material) and 445 g of distilled water were placed in an autoclave having an content of 13.6 L and substituted with nitrogen. Stirring was started from 190 ° C. and the internal temperature was raised to 250 ° C. over 4 hours. At this time, the autoclave was boosted to 3.1 MPa. After continuing the reaction for 1 hour as it was, the low-order condensate was extracted by releasing it into the atmosphere from a spray nozzle installed in the lower part of the autoclave. Then, after cooling to room temperature, it was pulverized with a pulverizer to a particle size of 1.5 mm or less, and dried at 110 ° C. for 24 hours. The ultimate viscosity [η] of the obtained low-order condensate was 0.15 dl / g. Next, this low-order condensate was placed in a shelf-stage solid-phase polymerization apparatus, and after nitrogen substitution, the temperature was raised to 220 ° C. over 2 hours. Then, the reaction was carried out for 4 hours, and the temperature was lowered to room temperature. The obtained aromatic polyamide (PA) resin had a melting point of 320 ° C. and an ultimate viscosity [η] of 1.1 dl / g.

A-2: Polybutylene terephthalate (PBT) resin Polyplastic Co., Ltd. "930HL" (reinforced product with 30% by mass of glass fiber) Melting point 225 ° C
A-3: Polypropylene (PP) resin "J105G" manufactured by Prime Polymer Co., Ltd. Melting point 160 ° C
B-1: Phenol Novolac DIC Corporation "TD-2090" (hydroxyl equivalent 105 g / equivalent, softening point 117-123 ° C)
B-2: "KA-1165" manufactured by Cresol Novolac DIC Corporation (hydroxyl equivalent 119 g / equivalent, softening point 117-130 ° C)

* The softening point of the phenol resin is measured at a temperature rise of 3 ° C./min using a ring-shaped softening point measuring device ASP-M4SP manufactured by Meiho. The hydroxyl group equivalent of the phenol resin is measured by a method based on the neutralization titration method specified in JIS K 0070 (1992).

C-1: Glass fiber (chopped strand, E glass, average fiber length 200 μm, average diameter 10 μm, surface-treated product with epoxy-based sizing agent)

x ・ ・ ・ Length of component in the direction parallel to the fine uneven surface of the metal member surface between two points from the top of the convex part to the top of the adjacent convex part y ・ ・ ・ Adjacent from the top of the convex part The length of the component in the direction perpendicular to the fine uneven surface of the metal member surface between the two points up to the bottom of the recess.

Claims (10)

A metal / resin composite structure formed by joining a surface-roughened metal member and a thermoplastic resin member composed of a thermoplastic resin composition.
The metal member is aluminum, copper, magnesium, iron, titanium or an alloy containing them.
The thermoplastic resin composition comprises a thermoplastic resin (A) having a melting point of 160 ° C. or higher and a phenol resin (B) with respect to 100 parts by mass of the thermoplastic resin (A). A metal / resin composite structure, which comprises molding a thermoplastic resin composition containing in the range of 0.05 to 20 parts by mass. The metal / resin composite structure according to claim 1, wherein the phenol resin (B) is a novolak type phenol resin. The metal / resin composite structure according to claim 1 or 2, wherein the phenol resin (B) has a hydroxyl group equivalent in the range of 80 to 200 g / equivalent. The metal / resin composite structure according to any one of claims 1 to 3, wherein the phenol resin (B) has a softening point in the range of 50 to 180 ° C. The metal / resin composite structure according to any one of claims 1 to 4, wherein the resin composition is a melt-kneaded product. The metal / resin composite structure according to any one of claims 1 to 5, wherein the thermoplastic resin member is obtained by melt-molding a thermoplastic resin composition. A method for producing a metal / resin composite structure in which a surface-roughened metal member and a thermoplastic resin member composed of a thermoplastic resin composition are joined.
The metal member is aluminum, copper, magnesium, iron, titanium or an alloy containing them.
A feature is that a thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 160 ° C. or higher and a phenol resin (B) is melt-molded on a metal member at a melting point of the thermoplastic resin (A) or higher. A method for manufacturing a metal / resin composite structure. The metal / resin composite according to claim 7, wherein the thermoplastic resin composition contains the phenol resin (B) in the range of 0.05 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). Method of manufacturing the structure. A thermoplastic resin composition used for a metal / resin composite structure formed by joining a surface-roughened metal member and a thermoplastic resin member composed of a thermoplastic resin composition.
The metal member is aluminum, copper, magnesium, iron, titanium or an alloy containing them.
The thermoplastic resin composition is formed by blending a thermoplastic resin (A) having a melting point of 160 ° C. or higher and a phenol resin (B) as essential components, with respect to 100 parts by mass of the thermoplastic resin (A). , The thermoplastic resin composition, wherein the phenol resin (B) is in the range of 0.05 to 20 parts by mass. A thermoplastic resin member used for a metal / resin composite structure formed by joining a surface-roughened metal member and a thermoplastic resin member composed of a thermoplastic resin composition.
The metal member is aluminum, copper, magnesium, iron, titanium or an alloy containing them.
The thermoplastic resin composition is formed by blending a thermoplastic resin (A) having a melting point of 160 ° C. or higher and a phenol resin (B) as essential components, with respect to 100 parts by mass of the thermoplastic resin (A). , The range of 0.05 to 20 parts by mass of the phenol resin (B).
A thermoplastic resin member, characterized in that the thermoplastic resin member is obtained by melt-molding a thermoplastic resin composition.

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